Catalysis is an important interdisciplinary technology in the chemical industry. Of all chemical and pharmaceutical products produced today, more than 85% of products are manufactured by catalytic processes. The application of heterogeneous catalysis is highly desirable in order to achieve green chemistry goals by minimizing separations. The activity of heterogeneous catalysts depends on various factors, such as surface area, pore size of the support, and particle size of the active metals on the support. Hierarchically porous catalysts have connecting pores with multiple length scales (Yuan, Z.-Y., et al., Su: Insights into hierarchically meso-macroporous structured materials. J. Mater. Chem. 2006, 16, 663; Yang, X.-Y. et al., Hierarchically structured functional materials: synthesis strategies for multimodal porous networks. Pure Appl. Chem. 2009, 81, 2265; Boissiere, C., et al., Aerosol route to functional nanostructured inorganic and hybrid porous materials. Adv. Mater. 2011, 23, 599; X.-Y. Yang, et al., Self-formation phenomenon to hierarchically structured porous materials: design, synthesis, formation mechanism and applications. Chem. Commun. 2011, 47, 2763). This provides superior mass diffusion that can in turn increase the accessibility of the fluids (reactants and products) during organic transformations. There is increasing interest in development of these materials, as the ability to separately control structure at the nanometer and micrometer length scales (Parlett, C. M. A., et al., Hierarchical porous materials: catalytic applications. Chem. Soc. Rev. 2013, 42, 3876) promises improvements in catalytic performance by tuning the structure of the catalyst.
Porous carbon is widely used in heterogeneous catalysis because of high surface area and large pore volume coupled with good chemical, thermal, and mechanical stability. Meso-macroporous carbons have been studied in important applications, such as adsorption, gas storage, separations, and electrochemistry as well as catalysis. Porous carbons are widely used as supports for catalytically active metals such as palladium (Pd), platinum (Pt), nickel (Ni), etc. Various approaches have been reported for the synthesis of hierarchically porous carbon support including catalytic activation of carbon precursors (A. Oya, et al., Formation of mesopores in phenolic resin-derived carbon fiber by catalytic activation using cobalt. Carbon 33, 1085 (1995); T. Kyotani, Control of pore structure in carbon. Carbon 38, 269 (2000)), carbonization of polymeric blends (J. Ozaki, et al., Novel preparation method for the production of mesoporous carbon fiber from a polymer blend. Carbon 35, 1031 (1997)), use of basic catalysts such as lysine (G.-P. Hao, et al., Lysine-assisted rapid synthesis of crack-free hierarchical carbon monoliths with a hexagonal array of mesopores. Carbon 49, 3762 (2011)), and the carbonization of resorcinol-formaldehyde or phenol-formaldehyde aerogels (J. Biener, et al., Advanced carbon aerogels for energy applications. Energy Environ. Sci. 4, 656 (2011)).
Recent reports describe the fine tuning of the textural properties of the carbon including meso-macroporosity, ordered-disordered, surface area, and stability by varying the composition of the surfactant template and carbon precursor or hard (C. Liang, Z. Li, and S. Dai: Mesoporous carbon materials: synthesis and modification. Angew. Chem.—Int. Ed. Engl. 20, 3696 (2008); Y. Xia, et al., Templated nanoscale porous carbons. Nanoscale 2, 639 (2010)), and soft-templating methods (L. Chuenchom, et al., Recent progress in soft templating of porous carbon materials. Soft Matter 8, 10801 (2012)). The use of SiO2 monoliths as a hard template for replication to synthesize mesoporous carbon monoliths has been reported (A.-H. Lu, J et al., Easy and flexible preparation of nanocasted carbon monoliths exhibiting a multimodal hierarchical porosity. Micropor. Mesopor. Mater. 72, 59 (2004)). Various block-copolymers and the tri-block copolymers of the Pluronic family have been applied for the direct synthesis of ordered porous carbon (C. Liang and S. Dai: Synthesis of mesoporous carbon materials via enhanced hydrogen-bonding interaction. J. Am. Chem. Soc. 128, 5316 (2006); F. Zhang, et al., A facile aqueous route to synthesize highly ordered mesoporous polymers and carbon frameworks with Ia3d bicontinuous cubic structure. J. Am. Chem. Soc. 127, 13508 (2005); C. Liu, et al., Facile synthesis of ordered mesoporous carbons from F108/resorcinol-formaldehyde composites obtained in basic media. Chem. Commun. 757 (2007)). The incorporation of active-metal species onto the porous carbon support is typically carried out by impregnation or infiltration techniques. However, these processes can be time consuming and increase the cost of the final product. What are thus needed are more efficient techniques for synthesizing hierarchically porous carbon monoliths containing active metal species, which can be used in a variety or catalytic or separation processes. The compositions and methods disclosed herein address these and other needs.